A lightweight, renewable three-layer co-laminated embossed material and its preparation process

Abstract

This application relates to the technical field of material processing and surface treatment, and discloses a preparation process for a lightweight, renewable, three-layer co-laminated embossed material. The middle layer of the three-layer co-laminated embossed material is obtained by mixing and foaming recycled waste with polyolefin foaming material. The steps are as follows: S1, the top layer, middle layer, and bottom layer are cleaned and dried, and an adhesive is applied to the side of the middle layer near the top layer and the side of the bottom layer near the middle layer; S2, the side of the top layer near the middle layer, the side of the middle layer and the side of the bottom layer without adhesive are heated by a heating roller. After heating, the co-lamination and embossing are completed simultaneously by extrusion between the back roller and the embossing roller to obtain the three-layer co-laminated embossed material. It has the advantages of realizing the utilization of renewable materials and improving the aesthetics of the embossed material.

Description

Technical Field

[0001] This application relates to the technical field of materials processing and surface treatment, and in particular to a lightweight renewable three-layer co-laminated embossed material and its preparation process. Background Technology

[0002] In the field of materials processing and surface treatment, embossing is an important means of decoration and functional enhancement, widely used in textiles, packaging, building materials, automotive interiors, and many other industries. Embossing generally uses steel plates or embossing rollers engraved with different patterns to press patterns or simulate the grain of animal hides onto leather or textile surfaces. Originally used to conceal defects in the original grain of leather to improve its usability, it is now primarily used to improve appearance and enhance aesthetics. Depending on the mold used, embossing processes can be plate-type or roller-type. Plate-type embossing machines are similar in form to plate ironing machines, consisting of a heated upper plate with an engraved pattern and a lower plate. The ironing action of the two plates presses the pattern onto the leather surface in the middle. Roller-type embossing machines consist of heated rollers with engraved patterns and pressure rollers. The leather is pressed into patterns as it passes between the rotating rollers.

[0003] However, both sheet metal embossing machines and roller embossing machines, based on traditional embossing processes, are often limited to processing single-layer and double-layer materials. But based on national green environmental protection requirements, even when renewable materials, such as recycled TPO, recycled PVC, or recycled TPU, are applied to single-layer or double-layer embossed materials, their aesthetic appeal remains insufficient. Summary of the Invention

[0004] In order to realize the utilization of renewable materials and improve the aesthetics of embossed materials, this application provides a lightweight renewable material three-layer co-attached embossed material and its preparation process.

[0005] In a first aspect, this application provides a preparation process for a lightweight, renewable, three-layer co-laminated embossed material, employing the following technical solution:

[0006] A process for preparing a lightweight, renewable, three-layer co-laminated embossed material, wherein the three-layer co-laminated embossed material comprises a top layer, an intermediate layer, and a bottom layer, wherein the intermediate layer is prepared by mixing and foaming recycled waste with polyolefin foaming material;

[0007] It includes the following steps:

[0008] S1. Clean and dry the top layer, intermediate layer and bottom layer, and apply adhesive to the side of the intermediate layer near the top layer and the side of the bottom layer near the intermediate layer.

[0009] S2. The side of the top layer closest to the middle layer, the middle layer and the side of the bottom layer without adhesive are all heated by heating rollers. After heating, the co-lamination and embossing are completed simultaneously by the extrusion between the back roller and the embossing roller, resulting in a three-layer co-lamination embossed material.

[0010] By adopting the above technical solution and the three-layer co-lamination process of this application, the recycled waste material layer can be wrapped, which can improve the aesthetics. Furthermore, by using a foamed layer of post-consumer and recycled materials as the middle layer, the density of the material is reduced, achieving the recyclability and lightweighting of the material. Moreover, by using three-layer co-lamination and simultaneous embossing, the production efficiency is greatly improved, meeting the national green and environmental protection requirements.

[0011] Preferably, the surface layer is further provided with a heating lamp on the side away from the intermediate layer for heating.

[0012] By adopting the above technical solutions, the embossing effect on the surface layer can be improved, and the boundaries of the embossed pattern can be made clearer.

[0013] Preferably, a heating lamp is provided above the adhesive-coated side of the intermediate layer and the bottom layer for heating.

[0014] By adopting the above technical solution, the adhesive is kept in a liquid state, maintaining its viscosity and delaying its curing time, thus improving the bonding effect.

[0015] Secondly, this application provides a lightweight, renewable, three-layer co-laminated embossed material, employing the following technical solution:

[0016] A lightweight, renewable, three-layer co-laminated embossed material is prepared using a process for preparing lightweight, renewable, three-layer co-laminated embossed materials.

[0017] By adopting the above technical solution, the production efficiency and product qualification rate of the three-layer co-bonded embossed material obtained by the three-layer co-bonding process provided in this application are both high.

[0018] Preferably, the recycled waste accounts for ≤70% by weight of the intermediate layer, and the intermediate layer is prepared as follows:

[0019] The recycled waste is crushed to obtain a crushed material with a particle size ≤3mm. The crushed recycled waste material and polyolefin foaming material are then mixed and foamed.

[0020] The polyolefin foaming material comprises the following raw materials in parts by weight: 45-55 parts of polyolefin elastomer, 35-45 parts of metallocene polyethylene, 35-45 parts of styrene-butadiene block polymer, 4-7 parts of microsphere foaming agent, 0.3-0.7 parts of foaming accelerator, 0.8-1.2 parts of crosslinking agent, 0.3-0.6 parts of co-crosslinking agent, 0.3-0.7 parts of surfactant, and 0.05-0.5 parts of anti-aging agent;

[0021] The surfactant is prepared by compounding poloxamer and sodium dodecylbenzenesulfonate, wherein the weight ratio of poloxamer to sodium dodecylbenzenesulfonate is (1-5):1.

[0022] By adopting the above technical solution, during polyolefin foaming, due to the influence of interfacial energy, the bubbles at the edges of the recycled pulverized material are relatively large, resulting in a large spatial separation between the recycled pulverized material and the polyolefin foaming material. This leads to poor mechanical properties in the resulting three-layer co-laminated embossed material. Poloxamer is a novel high-molecular-weight nonionic surfactant, a block copolymer of polyoxyethylene and polyoxypropylene ether, often used as a pharmaceutical excipient, such as an emulsifier and stabilizer in intravenous emulsions. The inventors of this application, by compounding it with sodium dodecylbenzenesulfonate and applying it to the intermediate layer polyolefin foaming system, found that it has excellent compatibility with the system, provides excellent foam stabilization, and can regulate foaming uniformity. This makes the bubbles at the edges of the recycled pulverized material uniform, significantly reduces the spatial separation at the edges of the recycled pulverized material, and improves the mechanical properties of the three-layer co-laminated embossed material. By controlling both the surfactant and the particle size of the recycled pulverized material, the mechanical properties of the three-layer co-laminated embossed material are greatly improved. The weight ratio of poloxamer to sodium dodecylbenzenesulfonate is a key factor affecting the mechanical properties of three-layer co-laminated embossed materials. When the weight ratio of poloxamer to sodium dodecylbenzenesulfonate is within this range, the synergistic effect between the two substances is better.

[0023] Preferably, the recycled waste pulverized material is soaked in a hydroxysilane coupling agent solution and then mixed with polyolefin foaming material for foaming.

[0024] By adopting the above technical solution, the compatibility between the recycled waste pulverized material and the polyolefin foam material can be improved after the recycled waste pulverized material is treated with a silane coupling agent. In addition, as an organosilicon substance, the silane coupling agent has a certain defoaming effect, which can eliminate larger air bubbles in contact with the recycled pulverized material, thereby reducing the separation between the recycled pulverized material and the polyolefin foam material, making the integrity of the intermediate layer higher, and thus making the mechanical properties of the three-layer co-laminated embossed material stronger.

[0025] Preferably, the adhesive is polyurethane foam.

[0026] By adopting the above technical solution, the polyolefin foaming agent is bonded to the polyolefin foam. When the back roller and embossing roller are squeezed, the polyolefin foam is co-bonded. Under the extrusion action, the polyolefin foam expands and impacts the top layer, middle layer and bottom layer, making the adhesive tightly bonded to each layer. This results in better overall integrity and excellent peel strength of the three-layer co-bonded embossed material.

[0027] Preferably, the thickness of the top layer is 0.1-0.4 mm, the thickness of the middle layer is 0.1-0.6 mm, and the thickness of the bottom layer is 0.1-0.4 mm.

[0028] Preferably, the top layer is a TPO single film, a PVC single film, or a TPU single film; the bottom layer is a TPO single film or a polyolefin foam layer; and the recycled waste is one or more of recycled TPO, recycled PVC, and recycled TPU.

[0029] In summary, this application includes at least one of the following beneficial technical effects:

[0030] 1. The three-layer co-lamination process of this application can wrap the recycled waste material layer, which can improve the aesthetics. Furthermore, the use of a foamed layer of post-consumer and recycled materials as the middle layer reduces the density of the material, achieving both recyclability and lightweighting. Moreover, the three-layer co-lamination and simultaneous embossing operation greatly improve production efficiency and meet national green and environmental protection requirements.

[0031] 2. During polyolefin foaming, due to the influence of interfacial energy, the bubbles at the edges of the recycled pulverized material are relatively large, resulting in a significant spatial separation between the recycled pulverized material and the polyolefin foaming material. This leads to poor mechanical properties in the resulting three-layer co-laminated embossed material. Poloxamer is a novel high-molecular-weight nonionic surfactant, a block copolymer of polyoxyethylene and polyoxypropylene ethers, often used as a pharmaceutical excipient, such as an emulsifier and stabilizer in intravenous emulsions. The inventors of this application, by compounding poloxamer with sodium dodecylbenzenesulfonate and applying it to the intermediate layer polyolefin foaming system, found that it exhibits excellent compatibility with the system, provides superior foam stabilization, and regulates foam uniformity. This results in more uniform bubbles at the edges of the recycled pulverized material, significantly reduces the spatial separation at the edges, and improves the mechanical properties of the three-layer co-laminated embossed material.

[0032] 3. This application uses recycled elastic waste to mix and foam with polyurethane, and through the co-lamination process of this application, the three-layer co-lamination embossed material can achieve a peel strength of 17.8 kg / mm ​​and a tensile strength of 79 MPa when the embossed pattern boundary is clear, complete and meets the requirements. At the same time, it has excellent wear resistance. Detailed Implementation

[0033] The following provides a more detailed description of this application in conjunction with specific details.

[0034] raw material

[0035] All raw materials used in the embodiments of this application can be purchased commercially.

[0036] Example

[0037] Example 1

[0038] A lightweight, renewable, three-layer co-laminated embossed material, comprising a top layer, an intermediate layer, and a bottom layer, is prepared using the following process.

[0039] S1. The intermediate layer is made from recycled waste through polyolefin foaming, and its preparation method is as follows:

[0040] The recycled TPO waste is washed, dried, and crushed to a particle size of less than 3 mm. The crushed recycled TPO and polyolefin foaming material are mixed and foamed, with a weight ratio of 5:3. The polyolefin foaming material includes 50 kg of polyolefin elastomer, 40 kg of metallocene polyethylene, 40 kg of styrene-butadiene block polymer, 6 kg of microsphere foaming agent, 0.5 kg of foaming accelerator, 1 kg of crosslinking agent, 0.4 kg of co-crosslinking agent, 0.5 kg of surfactant, and 0.1 kg of anti-aging agent.

[0041] The polyolefin elastomer used is POE, with the grade Mitsui Chemicals DF740; the metallocene polyethylene is polyethylene prepared using metallocene technology, with an average molecular weight of 45,000; the styrene-butadiene block polymer is hot-melt grade, with the grade 3540F; the surfactant is a mixture of poloxamer and sodium dodecylbenzenesulfonate in a weight ratio of 3:1, with poloxamer having an average molecular weight of 8,350, abbreviated as F68; the microsphere blowing agent is Matsumoto microsphere blowing agent F-36; the foaming accelerator is zinc stearate; the crosslinking agent is dicumyl peroxide; the co-crosslinking agent is diallyl terephthalate; and the anti-aging agent is antioxidant 1010.

[0042] The specific foaming method is as follows: Mix the raw materials of polyolefin foaming material, foam in a high-temperature furnace at a foaming temperature of 155℃, and after foaming, extrude through the discharge end of a single screw extruder to granulate and obtain recycled waste foaming material at an extrusion temperature of 160℃.

[0043] The recycled waste foam material is heated to 170℃ and melt-extruded to form a film with a thickness of 0.4mm, namely the intermediate layer;

[0044] S2. The top layer is a 0.3mm thick TPU single film, which is a TPU hot melt adhesive film; the bottom layer is a 0.1mm thick TPO single film; after cleaning and drying the top layer, middle layer and bottom layer, apply adhesive to the side of the middle layer near the top layer and the side of the bottom layer near the middle layer.

[0045] S3. The top layer, intermediate layer, and bottom layer are heated by heating rollers. After heating, the top layer, intermediate layer, and bottom layer are pressed and co-laid by back rollers and embossing rollers, while the embossing rollers emboss the top layer. In addition, a heating lamp is provided on the side of the top layer away from the heating rollers to heat it, which can make the embossing effect of the top layer better and the boundary of the embossed pattern clearer. Heating lamps are provided above the adhesive-coated side of the intermediate layer and the bottom layer to keep the adhesive liquid and sticky, so as to make the co-laying effect better. The temperature of the heating rollers and back rollers is 80℃, and the power of the heating lamps is 1000W.

[0046] Example 2

[0047] A lightweight renewable three-layer co-bonded embossed material differs from Example 1 in that its recycled TPO pulverized material is soaked in a 10% by mass ethanol solution of silane coupling agent, the silane coupling agent being bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, filtered, dried, and then subjected to polyolefin mixing and foaming. The remaining steps are the same as in Example 1.

[0048] Example 3

[0049] A lightweight, renewable, three-layer co-bonded embossed material differs from Example 2 in that the weight ratio of poloxamer to sodium dodecylbenzenesulfonate is 1:1, while the remaining steps are the same as in Example 2.

[0050] Example 4

[0051] A lightweight, renewable, three-layer co-bonded embossed material differs from Example 2 in that its poloxamer and sodium dodecylbenzenesulfonate have a weight ratio of 5:1, while the remaining steps are the same as in Example 2.

[0052] Example 5

[0053] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 2 in that the weight ratio of its recycled TPO pulverized material to polyolefin foam is 3:3, while the remaining steps are the same as in Example 2.

[0054] Example 6

[0055] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 2 in that the weight ratio of its recycled TPO pulverized material to polyolefin foam is 7:3, while the remaining steps are the same as in Example 2.

[0056] Example 7

[0057] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 6 in that the thickness of its middle layer is 0.6 mm, while the remaining steps are the same as in Example 6.

[0058] Example 8

[0059] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 2 in that its recycled TPO pulverized material is replaced with recycled PVC pulverized material of equal particle size, while the remaining steps are the same as in Example 2.

[0060] Example 9

[0061] A lightweight, renewable, three-layer co-bonded embossed material differs from Example 2 in that its recycled TPO pulverized material is replaced with recycled TPU pulverized material of equal particle size, while the remaining steps are the same as in Example 2.

[0062] Example 10

[0063] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 2 in that the middle and bottom layers are not heated by heating lamps, while the remaining steps are the same as in Example 2. Comparative Example

[0064] Comparative Example 1

[0065] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 1 in that it does not contain poloxamer in its surfactant, while the remaining steps are the same as in Example 1.

[0066] Comparative Example 2

[0067] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 1 in that sodium dodecylbenzenesulfonate is not added to its surfactant, while the remaining steps are the same as in Example 1.

[0068] Comparative Example 3

[0069] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 1 in that no surfactant is added to the polyolefin foam material during the preparation of the middle layer, while the remaining steps are the same as in Example 1.

[0070] Comparative Example 4

[0071] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 6 in that the thickness of its middle layer is 0.7 mm, while the remaining steps are the same as in Example 6.

[0072] Comparative Example 5

[0073] A lightweight, renewable, three-layer co-laminated embossed material differs from Example 1 in that its TPO pulverized material has a particle size range of 3-7 mm, while the remaining steps are the same as in Example 1.

[0074] Performance testing

[0075] Detection methods / test methods

[0076] Three-layer co-laminated embossed materials were prepared according to the preparation processes in Examples 1-10 and Comparative Examples 1-5, and then tested according to the following testing methods.

[0077] Peel strength: The three-layer co-laminated embossed material was cut into 25mm×150mm samples and tested using a tensile testing machine at a speed of 100mm / min.

[0078] Abrasion resistance: Tested according to the test method in QBT4195-2011, using H-22 grinding wheel, load 1kg, rotation speed 400 revolutions, to test whether the surface is worn through and the middle layer is exposed.

[0079] Tensile strength: Tensile tests were conducted using a universal testing machine at a tensile speed of 10 mm / min.

[0080] Table 1. Detection results of Examples 1-10 and Comparative Examples 1-5

[0081]

[0082] As can be seen from Examples 1-10, Comparative Examples 1-5, and the test data in Table 1, the three-layer co-laminated embossed material prepared by mixing recycled elastic waste with polyurethane and using the co-lamination process of this application, with clear and complete embossed pattern boundaries meeting the requirements, has a peel strength of 17.8 kg / mm ​​and a tensile strength of 79 MPa, while also exhibiting excellent wear resistance. Through multi-layer co-lamination and exquisite embossing, the appearance and market competitiveness of the product are greatly enhanced, meeting national green and environmental protection requirements. By using post-consumer and recycled material foam layers as the intermediate layer, the density of the material is reduced, achieving recyclability and lightweighting.

[0083] During polyolefin foaming, due to the influence of interfacial energy, the bubbles at the edges of the recycled pulverized material are relatively large, resulting in a significant spatial separation between the recycled pulverized material and the polyolefin foaming material. This leads to poor mechanical properties in the resulting three-layer co-laminated embossed material. Poloxamer is a novel high-molecular-weight nonionic surfactant, a block copolymer of polyoxyethylene and polyoxypropylene ether, often used as a pharmaceutical excipient, such as an emulsifier and stabilizer in intravenous emulsions. The inventors of this application, by compounding poloxamer with sodium dodecylbenzenesulfonate and applying it to the intermediate layer polyolefin foaming system, found that it exhibits excellent compatibility with the system, provides superior foam stabilization, and regulates foam uniformity. This results in more uniform bubbles at the edges of the recycled pulverized material, significantly reducing the spatial separation at the edges and improving the mechanical properties of the three-layer co-laminated embossed material. This is verified by the test data from Example 1 and Comparative Example 3. Combining the test data from Comparative Examples 1-2, poloxamer and sodium dodecylbenzenesulfonate have a synergistic effect and need to be added simultaneously to achieve the desired effect.

[0084] Based on the test data from Examples 1-2, it can be seen that treating the recycled pulverized material with a silane coupling agent can improve the compatibility between the recycled pulverized material and the polyolefin foaming material. Furthermore, as an organosilicon substance, the silane coupling agent has a certain defoaming effect, which can eliminate larger air bubbles in contact with the recycled pulverized material. In this application, a hydroxyl silane coupling agent is used, which can participate in the polyolefin foaming reaction, allowing the surface of the recycled waste material to participate in the polyolefin foaming reaction in situ. This reduces the separation between the recycled pulverized material and the polyolefin foaming material, resulting in a higher integrity of the intermediate layer. Consequently, the mechanical properties of the resulting three-layer co-laminated embossed material are stronger.

[0085] Based on the test data from Examples 2-4, it can be seen that the weight ratio of poloxamer to sodium dodecylbenzenesulfonate is a key factor affecting the mechanical properties of the three-layer co-laminated embossed material. The synergistic effect between the two substances is optimal when the weight ratio of poloxamer to sodium dodecylbenzenesulfonate is 3:1.

[0086] The test data from Examples 2 and 5-6 show that the higher the amount of recycled crushed material added to the intermediate layer, the lower the mechanical properties of the three-layer co-laminated embossed material. Considering the overall mechanical properties, the amount added should not exceed 70%. Combining Example 7 and Comparative Example 4, when the weight percentage of recycled crushed material added is 70%, the thickness of the intermediate layer should not exceed 0.6 mm.

[0087] The test data from Examples 2 and 8-9 show that recycled crushed materials, whether recycled TPO, recycled PVC, or recycled TPU, can all produce three-layer co-laminated embossed materials with excellent mechanical properties.

[0088] The test data from Examples 2 and 10 show that the heating lamp can enhance the adhesion between the top layer, the middle layer, and the bottom layer.

[0089] The test data from Example 1 and Comparative Example 5 show that the particle size of the recycled pulverized material should not be too large. When the particle size is large, the wettability and encapsulation of the polyolefin foam material on the recycled pulverized material are insufficient, resulting in poor mechanical properties of the three-layer co-laminated embossed material.

[0090] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. A lightweight, renewable, three-layer co-laminated embossed material, characterized in that: The three-layer co-laminated embossed material includes a top layer, an intermediate layer, and a bottom layer. The intermediate layer is prepared by mixing and foaming recycled waste with polyolefin foaming material. The preparation process of the three-layer co-laminated embossed material includes the following steps: S1. Clean and dry the top layer, intermediate layer and bottom layer, and apply adhesive to the side of the intermediate layer near the top layer and the side of the bottom layer near the intermediate layer. S2. The side of the top layer closest to the middle layer, the middle layer and the side of the bottom layer without adhesive are all heated by heating rollers. After heating, the co-lamination and embossing are completed simultaneously by the extrusion between the back roller and the embossing roller to obtain a three-layer co-lamination embossed material. The recycled waste material accounts for ≤70% of the weight percentage of the intermediate layer, and the intermediate layer is prepared as follows: The recycled waste is crushed to obtain a crushed material with a particle size ≤3mm. The crushed recycled waste material and polyolefin foaming material are then mixed and foamed. The polyolefin foaming material comprises the following raw materials in parts by weight: 45-55 parts of polyolefin elastomer, 35-45 parts of metallocene polyethylene, 35-45 parts of styrene-butadiene block polymer, 4-7 parts of microsphere foaming agent, 0.3-0.7 parts of foaming accelerator, 0.8-1.2 parts of crosslinking agent, 0.3-0.6 parts of co-crosslinking agent, 0.3-0.7 parts of surfactant, and 0.05-0.5 parts of anti-aging agent; The surfactant is prepared by compounding poloxamer and sodium dodecylbenzenesulfonate, wherein the weight ratio of poloxamer to sodium dodecylbenzenesulfonate is (1-5):

1.

2. The lightweight, renewable, three-layer co-laminated embossed material according to claim 1, characterized in that: The surface layer is also equipped with a heating lamp on the side away from the intermediate layer for heating.

3. The lightweight, renewable, three-layer co-laminated embossed material according to claim 1, characterized in that: Heating lamps are provided above the adhesive-coated side of the intermediate layer and the bottom layer for heating.

4. The lightweight, renewable, three-layer co-laminated embossed material according to claim 1, characterized in that: The recycled waste pulverized material is soaked in a hydroxysilane coupling agent solution and then mixed with polyolefin foaming material for foaming.

5. The lightweight, renewable, three-layer co-laminated embossed material according to claim 1, characterized in that: The adhesive is polyurethane foam.

6. The lightweight, renewable, three-layer co-laminated embossed material according to claim 1, characterized in that: The thickness of the top layer is 0.1-0.4 mm, the thickness of the middle layer is 0.1-0.6 mm, and the thickness of the bottom layer is 0.1-0.4 mm.

7. The lightweight, renewable, three-layer co-laminated embossed material according to claim 1, characterized in that: The top layer is a TPO single film, a PVC single film, or a TPU single film; the bottom layer is a TPO single film or a polyolefin foam layer; the recycled waste is one or more of recycled TPO, recycled PVC, and recycled TPU.

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